Plant growth regulant compositions and methods

ABSTRACT

Compounds of the type Cl-CH2CH2-Si O(CH2CH2O)3CH2CH3 3 are disclosed.

United States Patent Leeper et a1.

PLANT GROWTH REGULANT COMPOSITIONS AND METHODS Inventors: Robert W.beeper, Chalfont; Paul Strohm, Philadelphia, both of Pa.

Assignee: Amchem Products, Inc., Ambler, Pa.

Filed: Apr. 4, 1973 Appl. No.: 347,736

US. Cl 260/4483 R; 260/340]; 71/79;

71/88 Int. C07F 7/04; C07F 7/18 Field of Search 260/448.8 R, 340.7

[ Dec. 23, 1975 Primary ExaminerPaul F. Shaver Attorney, Agent, orFirm-Ernest G. Szoke; Michael E. Zall; Howard S. Ka'tzoff ABSTRACTCompounds of the type c|-cH,cH,-si O(CH,CH,0),CH,CH,

are disclosed.

5 Claims, No Drawings PLANT GROWTH REGULANT COMPOSITIONS AND METHODS Thepresent invention relates to composition and methods for regulating thegrowth of plants. And particularly, this invention concerns 2-haloethylsilanes and the use of compounds to induce, among other responses, butnot limited thereto, growth regulating responses which are ethylene orethylene-type responses.

The induction of an ethylene response in plant growth by other means hasbeen known for some time in the art. See, for example, "PlantBiochemistry" by James Bonner and .l. E. Vamer (I965), pages 641 to 664.

The particular mechanism by which ethylene affects the growth of plantsis not understood and has only recently been the subject of anyintensive investigation. However, it is clear that ethylene plays animportant role in regulating or participating in plant growth processes.It will be seen that the 2-haloethyl silanes of this invention containin their structures molecular configurations which are capable ofbreaking down in such a way as to release ethylene, although there is nointention to limit the present invention to this or any other theory. a

The use of certian other silane compounds outside the scope ofthepresent invention for the purpose of modifying certain aspects ofplant growth is known in the agricultural art.

ln US. Pat. No. 3,l83,076 the use of chloromethy-, l-chloroethylandvarious other alkoxysilanes for accelerating fruit maturity, defoliationand for herbicidal use is disclosed.

US. Pat. Nos. 3,390,976 and 3,390,977 together disclosehalomethyl-alltoxysilanes used as herbicides.

In an article entitled "Some l-lerbicidal Silicon Compounds", by J. K.Leasure and J. L. Speier, J. Med. Chem., 9,949 ([966), the herbicidaluse of several haloalkyl-silanes is described.

In contrast to the prior art just described, the present inventioninvolves inducing a plant growth regulating response or an ethylene-typeresponse through the application of compounds at the plant site havingthe following generic formula:

wheein X is chlorine or bromine; R is chloro-, alkyl, phenyl,chlorophenyl, benzyl, chlorobenzyl or the radical OR,; and wherein R,,R, and R are each independently selected from the group consisting ofpolyether of the formula (C,,H,,,O)-,,R wherein n 2 or 3, y may be anyinteger from 2 to I00, and R4 is a terminal group selected from thegroup consisting of 69 2 polyether units are possible, giving anextensive polymer chain substituent, the preferred range of size interms of number of basic repeated units has been found to be between 2and 20, and most preferably between 2 and [0.

By ketal is meant any reaction product of ketones and polyhydricalcohols. The term polyhydric alcohol is understood to mean an alcoholhaving two or more hydroxyl groups.

Silane compounds of the present invention which have also been foundcapable of inducing a plant growth regulating response or an ethylene orethylenetype response through application at the plant site, are thosehaving the following generic formula:

R" (It) wherein X is chlorine or bromine; R. has the same meaning as setforth above; and R and R" are each independently selected from the groupconsisting of alkyl, phenyl, chlorophenyl, benzyl and chlorobenzyl.

The silane compounds of this invention will be better understood fromthe following description of preferred methods of preparation of thecompounds, specific examples of which methods are set out furtherbelow.lt is understood, however, that this is exemplary only, and that thepresent invention is to be taken in its broadest sense, and notnecessarily limited in terms of the reactants, reaction temperature andpressure conditions, residence times, separation techniques and othermethod parameters by which the compounds of the present invention areprepared.

The silane comounds of the present invention which are comprised in partby the structural unit which may be represented as Si-O-R, wherein R isdefined as R above, may be prepared by the reaction of 3 moles(stoichiometric) of an hydroxyl compound having the desired R entitywith one mole (stoichiometric) of 2-chloroethyltrichlorosilane. Thedesired reaction product is formed and hydrogen chloride is liberated.This preparation method may be represented generally as follows:

JROH CICH,CH,SiCI,

ClCH,CH Si(OR); 'l' SHCI It will be noted that in this instance all ofthe bondings of groups to the silicon atom comprise the structural unit:Si O R.

The preparation method jsut described may be performed in a solventmedium. In such event, however, the hydrogen chloride gas which isevolved must be effectively removed..Thus, it,has provenadvantageous tovary the method by replacing the solvent medium with a tertiary aminesuch as pyridine, which is able to act as both a medium for thereaction, and as an effective hydrogen chloride acceptor. The hydrogenchloride salt of pyridine is formed readily, allowing the reaction to goto completion. It will be understood that other tertiary amines may beemployed as well, for example, N,N-alkyl substituted anilines, pyridinederivatives and trialkylamines.

Another variation of the preparation method described above which hasproven advantageous is one in which an excess of the hydroxyl compoundreactant is employed as a medium for the reaction. Thus, for example,methanol, ethanol and so forth, may be used 3,928,406 3 4 both as thereactant materials and, supplied in excess, considered that certaingrowth regulating responses are effective media in which the reactionmay proceed achieved through the practice of this invention may notreadily. be regarded, in a technical or traditional sense, as Othersilane compounds of the present invention known or yet to be discoveredethylene or ehtylenehave been described which are comprised in part bythe 5 type responses. Thus, it is preferred to regard the restructuralunit which may be represented as Si R, sults achieved in the practice ofthe present invention wherein R is defined as alkyl, phenyl,chlorophenyl, as growth regulating responses.

benzyl or chlorobenzyl. A compound of this invention In view of theforegoing, it can be seen that the term having the indicated structuralunit may be prepared by method for regulating plant growth or the termfirst reacting magnesium with R Br, where R is degrowth regulationprocess or the use of the words fined as set out immediately above. Thisreaction gives growth regulation"or other terms using the word theproduct RMgBr. This reaction product is in regulate as used in thespecification and in the claims turn reacted with2-chloroethyl;trichlorosilane to give mean a variety of plant responseswhich attempt to a compound of this invention which is comprised inimprove some characteristic of the plant as distinpart of the structuralunit: Si-R. It will be understood guished from herbicidal action, theintention of which that this method is a conventional Grignardsynthesis, is to destroy or stunt a growth of a plant. For this reasonand that by regulating preparation method conditions it the compoundsand their use in the practice of this is possible to obtain good ieldsof the products: invention are in such amounts that they arenonclCH,CH,-SiRCl, and C1 H,CH,SiR,Cl. phytotoxic with respect to theplant being treated.

It will be further understood that these reaction prod Despite thisfact. the silane compounds of this invem may be employed themselves asreactants in the tion can sometimes be used in a herbicidal context, forfirst prepalauon T' described whereby the example, to stimulate thegrowth of dormant rhizomes S'CII or porno f the P reacts in order tomake such rhizomes more susceptible to a hydmxyl compoun? to l has:structural herbicide. However, in such a context the silane como wheremClem/ed from, the hydorxyl pounds of the present invention are notthemselves in compound ROHi and defined as RI m the genenc any practicalsense herbicides since they promote the formula By using these l methodsl growth of the unwanted plant or otherwise make it described inSequence it is thus Posslble to Produce susceptible toatrueherbicide.Thus, the present invenany desired combination ofthe basicstructural units: Si tion can be carried out in conjunction with or inthe o R and Si R in a Single silane compound All presence of othercompounds or mixtures which are of these compounds, of course, willcontain the moiety herbicides xCH2,CH2 wherein X is bromo' or chlom" asBy virtue of the practice of the present invention a fined m the genencformf'las I and above' wide variety of plant growth responses, generallyethyl- In order that this invention may be better understood eneresponses or ethy|ene type responses have been silane cmpundsfFrmulasand achieved, including the following: inhibition of termil f R1 and/OrR2 and/or are defined as nal growth and control of apical dominance withan ketal afleneral mefhod of Preparanon for such increase in branching;abscission of foliage, flowers and pounds be descnbed fruit; hasteningof ripening and color promotion in Merely Y y of example and YI anylmemlon fruit; acceleration of senescence or ripening of leaves; ofthereby limiting the broad definitlon of ketal" as set 40 induct-Km offlowering and fruiting; and increasing the out above, such a substituentmay be prepared by relatex flow of rubberzplams actlng acetone withi,l,l-tnmethylolethane according will be apparent that other plantgrowth responses to the followmg reactlon: which are ethylene orethylene-type responses may be CH, O HOCl-l, H, H, CH, CH;

CH HOC( CH,OH C( -CH,/ \CH,OH

The reaction product will be seen to be an hydroxyl achieved with equalfacility by virtue of the practice of compound which may be employed asa reactant with the present invention. Such responses would include,

Z-chloroethyl-trichlorosilane to giveasilane compound for example, thefollowing: increasing yields; auxin ofthis invention which is comprisedin part of the strucactivity; changing bio-chemical compositions of thetural unit: Si O R, according to the preparation plant; abortion ofinhibition of flowering and seed demethod described above. It will alsoreadily be seen velopment; prevention of lodging; stimulation of seedthat many such ketal derivatives may be produced as germination andbreaking of dormancy; resistance to the reaction products of variousketones with various freeze injury; resistance to plant disease; hormoneor polyhydric alcohols. All such derivatives are within the epinastyeffects; and interactions with other growth scope of this invention.regulators.

The silane compounds of the present invention have A further descriptionof some of the aspects of these been found to exhibit a wide variety ofplant growth various plant growth responses will permit a betterregulating properties or ehtylene-type responses, deunderstanding of thepresent invention. pending upon the concentration used, the formulationInhibition of terminal growth and control of apical employed and thetype of plant species treated. While dominance has been produced inprivet (Ligustrum the compounds of the present invention may be viewedovalifolium).

as producing an ethylene or ehtylene-type response, While removal of thetop or apical bud by mechanithere is no intention to so limit theinvention, since it is cal means should in theory permit growth by thelateral or auxiliary buds, it has been found that when the apical bud isremoved that one of the auxiliary buds often takes over the activity andtherefore the dominance of the apical bud. However, it has been foundthat use of the silane compounds of the present invention usuallyretards the activity of the apical buds for a time, but then laterallows restoration of apical bud function and growth. Thus, it ispossible to avoid the permanent loss of buds inevitably associated withmechanical removal.

The silane compounds of this invention have been found to accelerate theabscission of mature foliage in cotton (Gossypium hirsutum). This isobviously of benefit as an aid to mechanical harvesting of cotton.Abscission of fruit following application of the silane compounds of thepresent invention has been observed in apples (Malus domestica).

Hastening of ripening of fruit has been produced using the silanecompounds of this invention in green fruit from tomato plants(Lycopersicon esculentum) and in green fruit of banana (Ananas comosus).It is also useful to employ the silane compounds of this invention toachieve color promotion in fruit which, although ripe, retains greencoloring. Thus, this invention is beneficial in removing the green colorfrom harvestable fruit and regreened fruit such as citrus fruit, forexample, lemons and oranges.

The practice of this invention has proven useful in accelerating thematurity or senescence of crops harvested for their leaves, particularlytobacco. The silane compounds of this invention have been found to beeffective for this purpose whether applied to the leaves beforeharvesting or soon after harvesting of the leaves.

Suitably applied, the silane compounds of this invention are capable ofincreasing flowering and fruiting in a number of economic crops. It hasbeen possible to achieve 100% flower induction in pineapple (Ananassativus) using the silane compounds of this invention.

The silane compounds of this invention have proven useful in stimulatingthe production and flow of various fluid components of plant systemswhich are transported throughout the plant. Some of these are ofconsiderable economic importance, such as the sap derived by tappingmaple trees, turpentine collected from pine trees, and latex collectedfrom rubber trees. It has been found that through the practice of thisinvention a dramatic increase in the yield of latex from rubber treesmay be achieved.

The silane compounds of this invention are capable of increasing yieldsof many plants, particularly, for example, small grains and various beanplants.

The silane compounds of this invention exhibit traditional auxinactivity. For example, they are capable of inducing bending of a planthypocotyl away from the side of application; they induce sprouting ofunderground rhizomes in both monocotyledonous and dicotyledonous plants;and they cause cell proliferation.

The biochemical composition of plants can be altered by applying to theplants, even after harvest of the plants or a portion thereof, effectiveamounts of the silane compounds of this invention. These modifica tionsof the biochemical content of plants include, but are not limited toprotein, carbohydrate, sugar, fat and nicotine content.

Application of the silane compounds of this invention will induce rigorresulting in firmer and stronger plants capable of resisting naturaltendencies toward lodging.

The silane compounds of this invention produce hormone or epinastyeffects on various plants, including notably tomatoes (Lycopersiconesculetum).

It is possible to use the silane compounds of this invention inconjunction with other plant growth regulators, such as maleichydrazide, N-dimethyl-aminosuccinic acid, naphthaline acetic acid andnaphthalene acetamide, gibberellic acid, 3-indoleacetic acid, 3-indolebutyric acid, and 2-chloroethylphosphonic acid.

The silane compounds of this invention may be used to promote diseaseresistance through increasing plant tissue resistance to invasion byplant pathogens by influencing the enzyme and other plant physiologicalprocesses which regulate natural disease immunity.

The silane compounds of this invention are viscous, high boiling liquidswhich will usually not distill without degradation. They are relativelyinsoluble in water, but can be dissolved in most organic solvents,including ketones, alcohols, hydrocarbons, chlorinated hydrocarbons andaromatic solvents. These silane compounds decompose rapidly on additionof alkali to yield ethylene gas.

When used as plant growth regulators, the silane compounds of thisinvention are preferably formulated with a suitable carrier or diluentor some combination of these. Such carriers or diluents are materialswhich can be organic or inorganic, naturally occuring or synthetic, withwhich the active ingredient is in some manner incorporated, tofacilitate its storage, transport, handling and application to theplants to be treated. The carrier material can be either solid or fluidand is preferably chemically and biologically inert. When the carriermaterial is a solid, it is preferably in particulate, granular orpelletized form, but other shapes and sizes may perform equally well.These solid carrier materials may be naturally occurring minerals whichhave been prepared for use by grinding, sieving, purification and othertreatments. Representative suitable mineral materials include thenatural clays, for example attapulgus, kaolin and bentonite clays;mineral silicates such as mica, vermiculite, talc and pyrophyllite;minerals in their natural forms as they are obtained from the earth, forexample, quartz, diatomaceous earth, fullers earth, chalk, rockphosphates and sulfates, calcium carbonates, and silica. syntheticallyproduced solid carrier materials, for example, synthetic hydrated silicaoxides, precipitated calcium silicate and synthetic magnesium silicatecan also be used. The material can also be an elemental substance suchas sulfur or carbon, preferably activated carbon.

Suitable solid carrier materials include organic flours, for example,wood, walnut shell, soybean, cottonseed, and tobacco flours, andfree-flowing hydrophobic starches.

Fluid carriers can be liquids, for example water, or a vaporous orgaseous material. Such carriers can be solvents or nonsolvents for theactive material.

The carrier can be mixed or formulated with the active material duringits manufacture or at any stage subsequently. The carrier can be mixedor formulated with the active material in any proportion depending onthe nature of the carrier. In addition, two or more carriers can be usedin combination.

The silane compounds of this invention can be concentrates containing,for example, from about 5 to about by weight of the active ingredient.These concentrates can be diluted with the same or different carrier toa concentration suitable for application. The

compositions of this invention may also be dilute compositions suitablefor application. In general, concentrations of about 0.] to about byweight of active material based on the total weight of the compositionare satisfactory, although lower and higher concentrations can beapplied if necessary.

The compounds of this invention can also be formulated as solutions ofthe active ingredient in an organic solvent or mixture of solvents, suchas for example alcohols; ethers', ketones, especially acetone;hydrocarbons and chlorinated hydrocarbons; aromatic solvents, especiallyxylene; and so forth.

The silane compounds of the present invention can also be formulated asemulsifiable concentrates which are concentrated solutions ordispersions of the active ingredient in an organic liquid, preferably awaterinsoluble organic liquid, containing an added emulsifying agent.These concentrations can also contain a portion of water, for example,up to about 50% by volume, based on the total composition, to facilitatesubsequent dilution with water. Suitable organic liquids include thoseselected from the group of organic solvents for the silane compounds ofthis invention set out above.

The emulsifying agent can be of the type producing water-in-oil typeemulsions which are suitable for application by low volume spraying, oran emulsifier of the type producing oil-in-water emulsions can be used,producing concentrates which can be diluted with relatively largevolumes of water for application by high volume spraying or relativelysmall volumes of water for low volume spraying. in such emulsions, theactive ingredient is preferably in a non-aqueous phase.

The emulsifying agent can be any suitable anionic or non-ionicsurfactant or a mixture of these two types of surfactants. Examples ofsuch mixtures are blends containing three parts of the calcium salt ofmyristyl-benzene sulfonic acid to one part of the oleate ester of apolyoxyethylene glycol (mol. wt. 350), or seven parts of the calciumsalt of laurylphenolsulfonic acid to three parts of monoor di-resin acidesters of polyoxyethylene glycol (mol. wt. 500). Other non-ionicsurfactants which are commonly blended with the anionic surfactants setout above include polyoxyethylene sorbitan monolaurate. Complex etheralcohols and various phosphate esters have also been found to be useful.Other suitable emulsifying agents will readily suggest themselves tothose skilled in the art. The emulsifying or surface active dispersingagents are generally employed in the liquid compositions in the amountof from I to percent by weight of the total composition weight.

Where application of the silane compounds of this invention are requiredto be topical, that is, applied to a specific situs of the plant and toremain there for a relatively extended period of time, it has beennecessary to provide a thickened formulation of the silane compounds.One suitable thickened formulation can be achieved by admixing with anyofthe silane compounds of this invention a stearate, such as, forexample, calcium stearate. Another suitable thickened formulation hasbeen achieved through the use of a heteropolysaccharide gum produced bythe fermentation of a carbohydrate by the bacterium i'uurlwmonascampesm's. To the mixture of any silane compound of this invention andthe heteropolysuccnaride gum is added a solvent and water in sufficientquantaties to produce the desired concentration of active ingredient, aswell as the desired qualities of viscosity and stability. Suitablesolvents include, among others, ethanol, butyrolactone and xylene. Tothis basic formulation may be added such adjuvants as lipids; forexample palm oil; anti-oxidants; bacteriostats and bark penetrants.

It will be understood that since the silane compounds of this inventionare liquids, that they may be applied directly to plants for the purposeof achieving plant growth regulator responses, without the necessity ofhaving added thereto any other material or materials, such as have beendescribed above.

It will be well understood by any plant biologist that, as with anyplant-growth regulator, the silane compounds of this invention should beapplied to any particular plant at certain optimum application rates,either of concentration in solution, or of weight per unit ground area,and at certain stages in the growth cycle of the plant, if they are toachieve any particular desired plant growth regulating effect. Thealmost limit less variety of plant species and the great diversity ofdesirable plant responses, together with the fairly wide range ofclimatic conditions which may be encountered, make it altogetherimpossible to specify exact application rates for all purposes. Suchapplication rates can, however, be determined fairly readily for anyparticular case by standard procedures well known in themselves.Generally, when applied broadcast to standing vegetation, theapplication rate for the plant growth regulating compositions of thisinvention will normally lie within the range of from 0.1 to I00 poundsper acre. It will be understood that the silane compounds of thisinvention vary considerably in molecular weight, particularly in view ofsuch possible substituents as the polyether groups. Thus, the amount ofthe silane compounds required for equivalent growth regulator activity,in terms of weight per unit of ground area, will represent a substantialrange of values. When applied on a weight amount per individual plantbasis, the application rate for the plant growth regulators of thisinvention will normally lie within the range of 10 to 3000 mg. perindividual plant. When applied by drenching trees or soaking seeds ortubers the application rate for the plant growth regulators willnormally lie within the range of from I to 50,000 parts per million(ppm.). Further detailed guidance in relation to a variety ofcommerically important agricultural uses will be found hereinafter.

It cannot be absolutely excluded that upon application of the silanecompounds of the invention in say aqueous solution they sometimesbreakdown outside the plant, while still in the aqueous solution inwhich they were applied, and the ethylene thus released is assimilatedby the plant in gaseous formbut this seems very improbable, since evenwhen stabilized against hydrolytic breakdown the silane compoundsaccording to the invention will to a greater or lesser extent exertplant growth regulating activity when applied to plants, as demonstratedfor instance by epinasty tests upon tomato plants.

It is therefore believed that the silane compounds of this inventionexert their growth regulating activity, at least in the great majorityof cases, by assimilation into the metabolic system of the plant.

It should be clear that it is a virtually impossible task to assay evenone of the silane compounds of this invention for growth responses inevery existing plant species. However, as will be seen from the manyexamples which follow, the present invention has been tested 9 on manyplant species for different growth responses. Nevertheless, there is nointention that this invention be limited to the species and responsesset forth, as in the future, workers in the art may find the presentinvention to be an effective growth regulant on other plants and for thegrowth responses.

However, it should readily occur to one skilled in the art that therecognition of improved results using the compounds of the presentinvention in connection with other plants, seeds, fruits and vegetablesnot specifically set forth herein is readily within the abilities of oneskilled in the art.

spray. The foliage was sprayed to run-off with 3.5 to 4 liters of spraysolution made up from an emulsifiable concentrate of the silane compoundto give a concentration of 1050 ppm. of silane compound in the totalspray solution.

Readings were taken at intervals of 4, 6, 8 and 11 days for redness(subjective 0-10 scale), abscission (pull force gauge in grams) andripeness (a cone point of about 100 microns radius reading in grams atskin penetration). On the eleventh day, the trees were shaken equallyand final readings of number of fruit dropped to total fruite borne weretaken. The results of these tests are summarized below.

Pull Force Subjective Ripeness Ripeness- Required Dropped RatingPressure for 2 Fruit Fruit Treatment Days: Test -Grams Days 7c 4 6 8 llGrams 4 6 8 it Check 0 0 O 3 I +l440+ 69 2-chl0roethyl-trisl 3 4 S 90l250+280 70 indication that full scale force required at minimum GROWTHINHIBITION EXAMPLE I FOLIAGE ABSCISSION EXAMPLE 3 Cotton plants weresprayed in duplicate with several silane compounds at the indicatedrates on June 2. The spray solutions were made up using the indicatedconcentration of active ingredient, with the carrier being acetone, 50%water and 0.1% Tween-20 surfactant, which is a polyoxyethylene/sorbitanmonolaurate mixture available from Atlas Industries, Wilmington, Del.Evaluations were made on June 26. A summary of the results are set outbelow.

Test Rate Number Growth Main Percent of Check (Unsprayed) Compound lb/Aof Basal Per Shoot Trunk Basal Growth Inhibition Shoots Cm. GrowthShoots Per of Main No. Cm. It it We Check 0 3.75 l3.7 37Z-chloroethyl-Irisl2 Z-methoxyethoxylethoxylsilane 50 1.3 29.8 I7 35 ll?54 2-chloroethyl-tris- {Hz-t2- ethoxyethoxy) ethoxy] ethoxy} -si|ane 6.4[1.6 I6 I60 58 'Ti inhibition I00 {treated growth X I00 check growth].

The data set out under percent growth inhibition of the p main trunk isthe main indicator of activity. However, a Cmcemmm" Defmumn Treatmentppm. I 1 Ave. high precentage of basal shoots relative to the check anda low percentage of growth per shoot (for all 60 0 30 shoots) is alsoindicative of activity and modifies to pm some extent the percent growthinhibition value. I -I Y- cthoxy)ethoxy]- silane U000 30 0 l5 FRUITABSCISSION Lchiomehfl 5 tris- 2-[2-(2- EXAMPLE 2 ethoxyethoxy) cthoxy]In this test red delicious apple trees on dwarftng stock ethoxy}-silane21700 20 It) IS Malling-9 were sprayed on September 14 with a back packsprayer adjusted for a rather coarse hollow cone FRUIT RIPENINGTreatment Rate Ratio of Ri Leaves Ave. EXAMPLE 4 MgJPIant to Total E shPlant Ri Green tomato fruit from Pixie Hybrid tomato plants I n Leavesgrown in the greenhouse were treated with spray solutions whichcontained the indicated concentrations g'fig 0 3/8 0/10 particularsilane compounds of this invention. Treaty ments were made on July 14and evaluations were fi y i yl 940 M 0113 28 made daily and concluded onJuly 31. These evalual0 tions are summarized in the data set out below.tris-{2-[2-(2- Number of Days from Treatment Concentration TreatmentUntil Pink Average ppm. I II III IV Days Check 0 l4 l92-chloroethyltris-[2-(2- methoxyethoxy) ethoxyl-silane l8800 9 9 l0 ll10 2-chlor0ethylwisp-[242- ethoxyethoxy) ethoxy] ethoxy} -silane 26000 77 I l 9 l l indication that fruit still green and taken to be dayscalculation of the mean.

ethoxyethoxy) ethoxyl ethoxy} -silane I320 2/9 2/10 5/14 27 EXAMPLE 5 30Green untreated banana fruit were sprayed to run-off (usually 5 ml.)with test solutions of particular silane FLOWER NDUCTION compounds ofthe present invention. The solvent-car- EXAMPLE 7 9 i z g employ? 3 of isurfalctan This test was replicated on 3 pineapple plants. P g ananad tig Twenty ml. of test solution was poured into the heart of f 2 if i 3? aan each plant. All of the test solutions were made up with T a eac rm 5g i '9 to true ye 0.1% Tween-20 surfactant and l0% acetone in water, I efi is l eefxpgnmem with the concentration of silane compound being as de ts o t e expel-men are 40 indicated. The treatment were made onDecember 16 Summar'ze e and the evaluations were made on February I. Thedata gathered from these evaluations is presented blow. TreatmentConcentration Days to Ripen for Average ppm. Each Fruit Days to I II IIIIV V Ripen Test 60 ml. Amount Ave. of

Compound per Plot Plants Induced Check mg Z-chloroethyltris-[ 2-( 2-Z-chloroethylmethoxyethoxy) tris-[2-( 2- ethoxy]-silane 6200 4 4 4 4 44.0 methoxyethoxy) 2-chloroeth lethoxyl-silane 900 l00 tris-{2-[2-( 5OZ-chIoroeth l ethoxyethoxy) tris-{2-[2-( ethoxy] ethoxy} ethoxyethoxy)-silane 8800 4 4 4 4 4 4.0 ethoxy] ethoxy} -silane 900 l00 Not yetripening in II) days.

TOBACCO LEAF RIPENING LATEX FLOW STIMULATION EXAMPLE 6 EXAMPLE 8 In thisevaluation Xanthii variety air cured tobacco The rubber plant varietyused for this test was PB-86, plants in 8 inch plastic pots in thegreenhouse were which had been planted in 1958. The tapping was donetopped and sprayed with 20 ml. of test solution having on Panel C usingan 8/2, d/2 tapping system. An area the indicated amount activeingredient. The test soluone inch below the tappinng cut was lightlyscraped tion contained the indicated amount of silane comand 2 grams ofeach formulation per tree was painted pound with the carrier being 10%of acetone, 0.l% on this scraped area with asmall brush. Each treatmentTween-20 surfactant, and the remainder water. The was replicated on 3trees. The silane compounds were plants were sprayed on November 19 andevaluated on Novemeber 23. The data derived from these evaluations isset out below.

specially formulated to produce a paint-like material by employing palmoil, propylene glycol, ethanol, water and a heteropolysaccharide gumthickener.

A total of 4 pretreatment tappings were made on April 3, 5, 7 and 9. Thetreatment applications were made on April 1 l. A total of4post-treatment tappings were made on April 14, 16, 19 and 23. A singlecollection was made from the pre-treatment tappings approximately 3hours after the trees were tapped. Two latex collections were made fromthe post-treatment tappings', the first collection was madeapproximately 3 hours after tapping and the second collection was made2-3 hours later. The data from this test is summarized below as theaverage ml. of latex per tree for 3 replications over the 4 tappingsbefore and after treatment.

of water was collected. The excess acetone and benzene were removed bydistillation. The residue was distilled under high vacuum. The reactionproduct distilled at 5862 C. at 0.25 mm. Hg. The refractive index wasdetermined and found to be 1.4492 (11 The yield of reaction product was23.3 g., which was a 58% yield.

B. Preparation of 2-chloroethyl-tris [(2,2,5-trirnethyl-5-m-dioxane)methoxy] -silane 2.0 g. (.01 mole) of 2-ch1oroethyl-trichlorosilane and2.4 g. (.03 mole) of pyridine were added slowly to a The Examples setout above are merely illustrative of the wide range of plant growthresponses which can be achieved in a variety of plant species using thesilane compounds of the present invention. It will be realized thatessentially similar effects can be secured with other silane compoundsdisclosed herein, particularly those specifically identified. It will beexpected in such a case, of course, that the rate of application mayrequire appropriate adjustment.

EXAMPLE 9 Preparation of 2-chloroethyl-tris-{2-[2-(2-ethoxyethoxy)ethoxy] ethoxy }-silane 73 grams of 2-chloroethyl-trichlorosilane and250 ml. of xylene were added to a one liter three-neck flask fitted witha stirrer, reflux condenser and an addition funnel. Ethoxytriglycol,197.3 g., was added slowly while the temperature was maintained at 40-50C. After the addition was complete, the mixture was refluxed withstirring for 2 hours. The hydrogen chloride gas which was evolved duringthe course of the reaction was removed through the top of the condenserand washed using a water scrubber. The xylene solvent was first removedby distillation, and then the unreacted ethoxytrigylcol was removed bydistillation at 70-73 C. at 0.25 mm Hg. vacuum. The yield of thereaction product was 191.3 g., or 83% yield. The refractive index of thereaction product was determined and was found to be 1.4528 U1 EXAMPLE 10A. Preparation of 2,2,S-trimethyl-S-m-dioxane methanol A well stirredmixture consisting of g. 1,1 ,l-trimethylolethane (0.25 mole), 36.7 ml.acetone, 160 ml. benzene and 0.5 g. p-toluenesulfonic acid was refluxedfor 8 hours using a Dean-Starke trap to collect the water formed duringthe course of the reaction. 5.6 ml.

well stirred solution of 2,2,5-trimethyl-5-m-dioxanemethanol in ml. oftoluene. The addition of pyridine was carried out in such manner that itslightly lagged the addition of the 2-chloroethyl-trichlorosilane. Awhite solid precipitated from the solution. After the additions werecomplete the reaction mixture was stirred for 1% hour. The pyridinehydrochloride formed was removed by filtration, and the solvent,toluene, was removed by distillation, first at atmospheric pressure, andthen under vacuum. The residue which remained was a viscous liquid. Thestructure of the reaction product was confirmed by means of infraredanalysis, the data from which is as follows: CH 1360 cm": Si- Ol 200 and1000 cm".

EXAMPLE 11 A. Preparation of 2-chloroethyl-diphenyl-chlorosilane 7.3 g.magnesium and 12 g. bromobenzene were added to 50 ml. of anhydrousdiethyl ether. A crystal of iodine was added and the ether began toreflux. After the reaction had started, 35.1 g. of bromobenzene wasadded slowly allowing gentle reflex of the reaction mixture. After theaddition was complete the mixture was refluxed for /6 hour. 500 ml. ofhexane was added, followed by the slow addition of 24.3 g. of2-chloroethyl-trichlorosilane. This mixture was refluxed with stirringfor 4 hours, cooled, then filtered to remove the inorganic magnesiumsalts which had been formed. The solvents were removed by distillationand the last traces by flash evaporation. The residue was distilledunder reduced pressure (1 mm. Hg.) at 98-l 10 C. The yield of reactionproduct was 7 g.

B. Preparation of 2-chloroethyl-diphenyl-methoxysilane 1.5 g. of 2chloroethyl-dipheny1-ch1orosilane, prepared as set out in A. immediatelyabove, was added to 10 ml. of methanol. The mixture was evaporated todryness yielding 1.2 g. of a viscous liquid. The reaction product wasanalyzed using infrared, which yielded the following data: AromaticC=C-l580 and 1460 cm;

SiO 1100 cm.

TABLE I Physical Constants Refraction Index X R =R,=R,,: b.p."C m," IR

Cl CH;,OCH,CH,OCH,CH, viscous SiO-llOO liquid Cl CH CH,O(CH,CH,O),CH CH,l.45l9 SiO-llO0 Cl HOCH,CH,O(CH,CH,O),CH,CH [.4570 Oil-3350 SiO-llOO ClHOCHgCHgO)CH CHg )lgCHgCHg 1.4662 Oil-3350 SiO-llOO Cl CH,OCHCH,OCHCH,

CH H l.4393 SiO-l 100 Cl CIQOCHfllLOCHfll-L- [.5480 Ar.C=C-

1515-1460 C,H O-l24O SiO-llOO Cl HO(CH,CHO) CH, H- OH-3650 Cli -I360 HCH, 1.4490 SiO-ll40 -ll)l0 Cl CH,OCH,CH,O(CH,CH,O),,CH,CH, l.4605Si0-ll00 Cl CH; OCH, CH, CH l360 viscous S|O-l200 CH, O-CH, CH,- liquid4000 Cl CH C OCH, C H

ci-u o-cm SiO-llOO Cl HOCH, CH,

viscous i-iocm cH, liquid X R =R,: R Cl CH HO(CH,CH,O),CH=CH, 1.46520H-3300 SiO-llOO Cl CH, CH CH,O{CH,CH,O) CH,CH,- l.5070 SiO-llOO ClOCH,CH, CH,,CH,O(CH,CH,),CH,CH, 1.52l6 Ar.C=C-l5l8 4480 C-C-l240SiO-llOl) TABLE II XCH,CH --Si'R Refrac. Index x R=R': R, b.p.C lR

Cl Q CH viscous Ar.C=C-l580 liquid -l460 SiO-llOO Cl HOCH,CH 0CH,CH,-viscous l-l0-3400 liquid Ar lS80-l460 SiO-HOO Cl H(OCH CH,) viscousHO-3400 4.5 liquid Ar.C=C'lS70 l 470 SiO-l I00 What is claimed is: 1.Compounds of the formula wherein X is chlorine or bromine; R is selectedfrom the group consisting of polyether of the formula -(C H ,,O) Rwherein n 2 or 3, y may be any integer from 2 to I00, and R is aterminal group selected from the group consisting of hydrogen, alkyl,phenyl, chlorophenyl; benzyl and chlorobenzyl; and ketal; and wherein Rand R are each independently selected from the group consisting ofalkyl, phenyl, chlorophenyl, benzyl and chlorobenzyl.

2. Compounds of the formula:

OR, XCl-l,-CH StOR,

wherein X is chlorine or bromine; and wherein R is a polyether of theformula (C,.H2,.O),,R4 wherein n=2 or 3, y may be any integer from 2 to100, and R is a terminal group selected from the group consisting ofhydrogen, alkyl, phenyl, chlorophenyl, benzyl and chlorobenzyl.

3. The compound2-chloroethyl-tris{2-[2-(2-ethoxyethoxy)ethoxy]ethoxy}-silane of theformula:

4. The compound 2-chloro-ethyl-tris-[2-(2-methoxyethoxy)ethoxy]-silaneof the formula:

O(CH,CH,O)z n Cl-CH,CH SiO(CH CH ohCH otcmcmoncn i 5. Compounds of theformula 20 XCH,CH,Si\-OR,

wherein X is chlorine or bromine; R is chloro-, alkyl, phenyl,chlorophenyl, benzyl, chlorobenzyl or the radical -OR;; and wherein R Rand R are each independently selected from the group consisting ofpolyether of the formula (C,,H ,,O-) ,R wherein n 2 or 3, y may be anyinteger from 2 to 100, and R is a terminal group selected from the groupconsisting of hydrogen, allcyl, phenyl, chlorophenyl, benzyl andchlorobenzyl', and ketal.

1. COMPOUNDS OF THE FORMULA
 2. Compounds of the formula:
 3. The compound2-chloroethyl-tris-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)-silane of theformula:
 4. The compound2-chloro-ethyl-tris-(2-(2-methoxy-ethoxy)ethoxy)-silane of the formula:5. Compounds of the formula